Electrochemical deposition apparatus and methods of using the same

ABSTRACT

An electrochemical deposition apparatus and methods of using the same are provided herein.

FIELD OF THE INVENTION

The present invention relates generally to devices and methods for theelectrochemical deposition of coating materials and more particularly,but not exclusively, to devices and methods for the electrochemicaldeposition of electrochromic polymers for the preparation ofelectrochromic lenses.

BACKGROUND OF THE INVENTION

Electroplating systems are commonly used to electroplate orelectrochemically deposit various materials onto conductive substrates.Although many types of electroplating systems are known, a variety ofproblems exist in the field, as briefly enumerated below, which arecurrently in need of solutions.

Certain problems present in the field include an inability to makeeffective electrical contact with substrates while, at the same time,insulating points of electrical contact from a deposition or platingsolution and maintaining a liquid seal in the deposition tank, such thatthere is no leakage. This may be a problem when using substrates withlower conductivity.

Moreover, problems may emanate from the resistance increase (orconductivity drop) from the point of electrical contact to the interiorof the substrate, especially acute for substrates with lowerconductivity. Due to this, the voltage applied at the point ofelectrical contact may not be the same as that seen at the interior ofthe substrate, leading to non-uniform deposits, with, in many cases, agreater thickness of the deposit nearer the point of electric contactthan that in the interior of the substrate.

The field also includes systems that lack an adequate means of holdingelectrodes and substrates firmly and maintaining precise and,preferably, minimal distance between the working electrode (thesubstrate upon which a material of interest may be deposited), thecounter electrode, and the reference electrode (if used), for effective,diffusion-limited control as well as high efficiency of theelectrochemical deposition.

Issues in the field also include the maintenance of a larger area forthe counter electrode as compared to the working electrode, so that thelimiting electrode processes for the deposition do not occur at thecounter electrode.

Additional limitations in the field include: (1) use of pumps andelaborate circulation systems which limit efficiency; (2) a lack of ahermetic seal of the deposition apparatus or plating tank such thatthere is minimal solvent loss, which is especially pertinent whenvolatile solvents are used; (3) a lack of accurate control of theapplied potential at the working electrode; (4) a lack of accuratecontrol of the total charge passed during electrochemical deposition, sothat thickness, morphology, and other features of the deposit may bewell controlled; and (5) a lack of amenability to automated orsemi-automated electrochemical deposition.

The present invention answers these and other needs in the field andprovides an electroplating device and methods of using the same.

SUMMARY OF THE INVENTION

Generally, the present invention provides an apparatus for theelectrochemical deposition (e.g., electrochemical polymerization,electrochemical plating, or electroplating) of a coating material from adeposition solution. In a particular embodiment, the present inventionpertains to an electrochemical deposition apparatus configured todeposit monomers of electrochromic conducting polymers at a substrate.

In a first aspect, the present invention provides an electrochemicaldeposition apparatus that may include a support structure. The apparatusmay include a first electrode mount connected to the support structureand a second electrode mount connected to the support structure. Theapparatus may include a deposition chamber frame that may be configuredto receive a deposition solution. The deposition chamber frame may bedisposed proximate to the first and second electrode mounts. Moreover,the deposition chamber frame may include a first aperture portion and asecond aperture portion. The first aperture portion may be configured toface the first electrode mount and may include a first aperture and aconductive perimeter element. The second aperture portion may beconfigured to face the second electrode mount and may include a secondaperture.

In certain embodiments of the apparatus of the invention, the apparatusmay include at least one biasing member that may connect the supportstructure to at least one of the first electrode mount and the secondelectrode mount. The at least one biasing member may include a spring, aclamp, an actuator, or a combination thereof. For example, the at leastone biasing member may connect the support structure to the firstelectrode mount and may include a pneumatic actuator.

Regarding certain features of the deposition chamber frame, the secondaperture may be larger than the first aperture.

The apparatus of the invention may include a first electrode connectedto the first electrode mount. The first electrode may be configured tobe disposed in electrical communication with the conductive perimeterelement at the first aperture portion. Moreover, the first electrode mayinclude a material selected from the group consisting ofindium-tin-oxide (ITO), poly (ethylene terephthalate) (PET), glass, anda combination thereof (e.g., a conductive plastic ITO/PET).Additionally, the first electrode may include or be provided as aconductive sheet (e.g., a conductive sheet that includes one or more ofITO, PET, and glass).

Regarding the conductive perimeter element, the element may include atleast one electrode contact. The at least one electrode contact mayinclude a plurality of electrode contacts. Alternatively, the at leastone electrode contact be a continuous electrode contact. In certainembodiments, the conductive perimeter element may include a plurality ofcontact pins (e.g., spring-loaded contact pins).

The apparatus of the invention may include a second electrode connectedto the second electrode mount. The second electrode may includegraphite. For example, the second electrode may include a conductivesheet composed of graphite.

In another embodiment, the apparatus of the invention may include firstand second electrodes that may be connected to the first and secondelectrode mounts, respectively, wherein the first electrode includes aworking electrode and the second electrode includes a counter electrode.

The apparatus of the invention may include a reference electrode thatmay be disposed within the deposition chamber frame. The referenceelectrode of the invention may be a Ag/AgCl reference electrode or a Ptor Au wire quasi-reference electrode.

In another aspect, the present invention may include an electrochemicaldeposition apparatus that includes an electroplating vessel. Theapparatus may include a support structure and a frame that may bedisposed with the support structure. The frame may include a cavity thatmay be configured to receive a deposition solution and may include: (1)a first aperture portion having a first aperture; and (2) a secondaperture portion having a second aperture, wherein the second aperturemay be larger than the first aperture. Moreover, the apparatus mayinclude a working electrode that may be disposed proximate to the firstaperture and/or a counter electrode that may be disposed proximate tothe second aperture. The frame, the working electrode, and the counterelectrode may be combined to form the electroplating vessel of theapparatus.

Regarding the cavity of the frame, the cavity may include a telescopedcavity, a tapered cavity, or a combination thereof. Additionally, thesecond aperture may be at least twice as large as the first aperture.Indeed, the second aperture may be three times as large as the firstaperture.

In certain embodiments, the apparatus of the invention may include aplurality of guides that are configured to align the frame, the workingelectrode, and/or the counter electrode.

In certain specific aspects of the devices of the invention, a counterelectrode and a working electrode may be provided that may be positionedto act as two walls of a deposition chamber. The counter electrode andworking electrode may be placed against a deposition frame portionwhich, in combination with the two electrodes, may act as the depositionchamber, vessel, or tank. Electrical contact may be made to the counterelectrode along its outside perimeter, which may be sealed off from thedeposition solution. The deposition solution may include a coatingmaterial. Electrical contact may be made to the working electrode alonga portion of the working electrode through the use of a conductiveperimeter element (e.g., spring-loaded contacts) that may also be sealedoff from the deposition solution. The deposition frame portion, whichmay be abutted by the working and counter electrodes, may be tapered ortelescoped such that the counter electrode area is larger than theworking electrode area. For example, the counter electrode area may besignificantly larger (e.g., at least two times larger) than the workingelectrode area so that the limiting electrode processes do not occur atthe counter electrode.

A reference electrode may also be disposed between the working andcounter electrodes. Preferably, the reference electrode is placed closerto the working electrode, rather than the counter electrode, such thatthe applied potential at the working electrode is more accuratelyregulated. Prior to filling or charging of the deposition vessel, thevessel may be sealed pneumatically as the counter and working electrodesare pneumatically biased against the deposition frame portion.

Deposition may be carried out and monitored using an applied-potentialalgorithm that may be specifically tailored to the material to bedeposited at the working electrode (e.g., a conducting polymer (CP)deposited via electropolymerization at the working electrode from adeposition solution that contains monomers of the CP). At the completionof the deposition, the deposition solution may be drained and thedeposition chamber may opened, thus opening the vessel, from which thesubstrate (i.e., the working electrode), may be removed for furtherprocessing. The exemplary device described herein, as well as theprocess related to the use of the same, may be amenable to automationand provides a solution to the needs in the field as outlined above.

In another aspect, the present invention includes a method forelectrochemically depositing a coating material on a working electrodewith an electrochemical deposition apparatus of the invention. Themethod may include mounting a working electrode at a first electrodemount of the apparatus. The method may include mounting a counterelectrode at a second electrode mount. In addition, the methods of theinvention may include preparing a deposition chamber by (1) biasing theworking electrode against a first aperture portion of a depositionchamber frame; and/or (2) biasing the counter electrode against a secondaperture portion of the deposition chamber frame. The methods of theinvention may also include the step of providing a deposition solutionto the deposition chamber, where the deposition solution may include thecoating material. The methods of the invention may then include applyinga potential across the working electrode and the counter electrode toelectrochemically deposit the coating material at the working electrode.Additionally, the methods of the invention may include removing theworking electrode, having the coating material deposited thereon, fromthe first electrode mount.

In one embodiment, the methods of the invention may include providingthe deposition solution to the deposition chamber by gravity flowing thedeposition solution to the deposition chamber from a container that isin fluid communication with the deposition chamber by raising thecontainer above the deposition chamber.

In another embodiment, the methods of the invention may include the stepof removing the deposition solution from the deposition chamber bygravity flowing the deposition solution to the container from thedeposition chamber by lowering the container below the depositionchamber.

The step of applying a potential across the working electrode and thecounter electrode, according to the methods of the invention may includeapplying a linear scan applied potential, which may include scanning theapplied potential from a pre-determined initial potential to apre-determined final potential at a pre-determined scan rate.Alternatively, or in addition thereto, the step of applying a potentialacross the working electrode and counter electrode, according to themethods of the invention, may include applying a fixed applied potentialor multiple fixed applied potentials, which may include applying (a)pre-determined fixed potential(s) until: (1) a pre-determined totalcharge is achieved; or (2) a pre-determined total deposition time haselapsed.

The step of preparing the deposition solution chamber may include atleast one of: (1) pneumatically biasing the working electrode againstthe first aperture portion of the deposition chamber frame; and (2)pneumatically biasing the counter electrode against the second apertureportion of the deposition chamber frame.

The present application incorporates several references that describecertain aspects of electrochromic technology, specifically, U.S. Pat.Nos. 5,995,273; 6,033,592; and 8,902,486; and U.S. Patent ApplicationPublication Nos. 2013/0120821 and 2014/0268283, the entirety of whichare incorporated herein by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing summary and the following detailed description of theexemplary embodiments of the present invention may be further understoodwhen read in conjunction with the appended drawings, in which:

FIG. 1 schematically illustrates a perspective view of an exemplaryelectrochemical deposition apparatus of the invention.

FIG. 2 schematically illustrates an exploded view of an exemplaryelectrochemical deposition apparatus of the invention.

FIG. 3 schematically illustrates a perspective view of a tank supportmember.

FIG. 4 schematically illustrates a perspective view of an exemplaryworking electrode.

FIG. 5 schematically illustrates a perspective view of an exemplarycounter electrode.

FIG. 6 schematically illustrates a view of the second aperture portionon the deposition chamber frame of the invention.

FIG. 7 schematically illustrates a view of the first aperture portion onthe deposition chamber frame of the invention.

FIG. 8 schematically illustrates a method of using an electrochemicaldeposition apparatus of the invention to deposit a coating material on aworking electrode (i.e., a substrate).

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates generally to electrochemical deposition(e.g., electrochemical polymerization or “electroplating”) of coatingmaterials from deposition solutions onto desired substrates in a tank orvessel. More particularly, the present invention relates to theelectrochemical deposition of electrochromic conducting polymers fromtheir monomer containing solutions onto a conductive substrate using atank or vessel that facilitates automation of an electrochemicaldeposition process. These features include, by way of example, but notlimited to, pneumatic opening/closing and sealing of the tank or vessel,minimization of monomer solution volume, and devices for electricalconnection to substrates that minimize or reduce resistive drop.

Referring now to the figures, wherein like elements are numbered alikethroughout, FIGS. 1 and 2 provide an exemplary electrochemicaldeposition apparatus 1. The apparatus 1 includes a support structure 10.A first electrode mount 20 and second electrode mount 30 may beconnected to the support structure 10. The first electrode mount 20 andsecond electrode mount 30 may be used to mount electrodes upon whichelectrochemical deposition may occur. A deposition chamber frame 40 maybe placed proximate to the first electrode mount 20 and the secondelectrode mount 30. The deposition chamber frame 40 may be placedbetween the first electrode mount 20 and second electrode mount 30 suchthat when the first electrode mount 20 and the second electrode mount 30are biased against the sides of the deposition chamber frame 40, theymay combine to form a deposition chamber or vessel, which may receive adeposition solution.

When the first electrode mount 20 and second electrode mount 30 areseparated from the deposition chamber frame 40, the apparatus 1 is inits “open” configuration, during which an electrode may be placed on thefirst electrode mount 20 or second electrode mount 30. When the firstelectrode mount 20 and second electrode mount 30 are biased against thesides of the deposition chamber frame 40, thereby forming a depositionchamber or vessel, the apparatus 1 is in its “closed” configuration,during which the vessel may be filled with a deposition solution asdescribed herein.

The support structure 10 may include several components that support oneor more of the first electrode mount 20, the second electrode mount 30,and the deposition chamber frame 40. The support structure 10 mayinclude a base 11, support plates 13 and 14, a support member 15, andbrackets 12. As shown in FIG. 1, the support plates 13 and 14 may bepositioned on the base 11 and supported by brackets 12. The supportmember 15 may be positioned at the base 11, proximate to the supportplates 13 and 14. Specifically, the support member 15 may be placedbetween the support plates 13 and 14 and may support one or more of thefirst support mount 20, the second electrode mount 30, and thedeposition chamber frame 40. In particular embodiments, the supportmember 15 is fixed to the base 11 and is provided to support firstelectrode mount 20 and/or the deposition chamber frame 40 when theapparatus 1 is in its closed configuration. As shown in FIG. 3, thesupport member 15 may include a basin 151 and a drain 152. The basin 151may catch any deposition solution that escapes the deposition chamberframe 40 during operation of the apparatus 1. Moreover, the drain 151may allow any deposition solution caught within the basin 151 to beremoved or collected.

The components of the support structure 10 may be composed of a metal(e.g., aluminum), a polymeric material (e.g., high density polyethylene(HDPE)), or a combination thereof. In certain preferred aspects, thecomponents of the support structure 10 may be composed of aluminum. Forexample, the base 11, support brackets 12, support plates 13 and 14, andvessel support member 15 may be composed of aluminum.

The first electrode mount 20 may be connected to the support plate 13and the second electrode mount 30 may be connected to the support plate14. One or both of the first electrode mount 20 and second electrodemount 30 may be connected to support plates 13 and 14, respectively,through a biasing member 16. For example, both the first and secondelectrode mounts 20 and 30, respectively, may be connected to thesupport plates 13 and 14, respectively, through a biasing member 16. Incontrast, one of the first and second electrode mounts 20 and 30,respectively, may be connected to the support plate 13 or 14 via abiasing member 16 while the other electrode mount is connected to theother support plate by a fastener. As used herein, the term “fastener”refers to something that attaches or joins two or more parts together.In some embodiments, a fastener may be a mechanical fastener thatmechanically joins or affixes two or more objects together (e.g., ascrew, a pin, a rivet, and the like). In other embodiments, a fastenermay be a chemical fastener that that chemically joins or affixes two ormore objects together (e.g., glue, epoxy, adhesive, solder, and thelike). In an exemplary embodiment, the first electrode mount 20 may beconnected to the support plate 13 via one or more biasing members 16 andthe second electrode mount 30 may be connected to support plate 14 withone or more fasteners.

As shown in FIGS. 1 and 2, the present invention may include severalbiasing members 16. The term “biasing member” may represent a spring, aclamp, an actuator, or a combination thereof. When the biasing member isan actuator, the actuator may be a hydraulic actuator, a pneumaticactuator, or a combination thereof. In certain embodiments, the biasingmember 16 is a pneumatic actuator as shown in FIGS. 1 and 2. Inaccordance with the present invention, hydraulic and/or pneumaticactuators may be connected to a source of hydraulic and/or pneumaticpressure and a switch that may activate (extend) and/or deactivate(retract) such hydraulic and/or pneumatic actuators.

Moreover, the apparatus 1 may include 1 to 10 biasing members.Preferably, the apparatus 1 may include 4 to 6 biasing members, wherethe biasing members are pneumatic actuators. The biasing members 16 ofthe invention may be used to open and close the apparatus 1 as describedabove.

The first electrode mount 20 and the second electrode mount 30 may becomposed of a chemically inert polymeric material, such as HDPE.Moreover, each of the first electrode mount 20 and the second electrodemount 30 may include a flexible backing material on their respectivemounting faces 22 and 32. The flexible backing materials may be a sheetthat includes ethylene propylene diene monomer (EPDM), silicone rubber,or a combination thereof.

A first electrode 25 may be mounted on the first electrode mount 20. Anexemplary first electrode 25 is provided in FIG. 4. The first electrode25 may include a conductive sheet or film upon which a coating materialmay be deposited during an electrochemical reaction. The first electrode25 may include a metallic material, a non-metallic material, or acombination thereof, provided that the electrode is conductive. Forexample, the first electrode 25 may include a material selected from thegroup consisting of indium tin oxide (ITO), poly ethylene terephthalate(PET), glass, or a combination thereof. In a specific embodiment, thefirst electrode 25 may include a sheet or film of ITO/PET or ITO/glass.Moreover, the first electrode 25 may have a surface resistivity of about20 to 100 Ohms per square.

In another embodiment of the invention, the first electrode 25 may beshaped in the form of a lens, such as an eyeglass lens, in preference toa simple rectangular, circular, or oval shape, such that it is preparedfor assembly into a lens without the need for further cutting orshaping.

The second electrode 35 may be mounted on the second electrode mount 30.An exemplary second electrode 35 is provided in FIG. 5. The secondelectrode 35 may include a conductive sheet or film. The secondelectrode 35 may include a metallic material, a non-metallic material,or a combination thereof, provided that the electrode is conductive. Byway of non-limiting example, the second electrode 35 may includegraphite, gold, or platinum. In a specific embodiment, the secondelectrode 35 may be a conductive sheet of graphite. Moreover, as shownin FIG. 5, the second electrode 35 may include contact site 37. Thecontact site 37 may be a tab or portion of the second electrode 35 thatis amenable to attaching a clip, clamp, wire, or a combination thereof.

As described herein, the first electrode 25 is preferably the workingelectrode. In the present invention, the working electrode is thesubstrate upon which a coating material may be deposited during anelectrochemical reaction. The second electrode 35 is preferably thecounter electrode. In the present invention, the counter electrode isprovided to complete the electrochemical cell. Accordingly, where theworking electrode is configured to be a cathode, the counter electrodewill be the anode, and vice versa.

The first electrode 25 and second electrode 35 may include guide holes26 and 36, respectively. The guide holes 26 and 36 may be aligned withguide holes 24 and 31 on the first electrode mount 20 and secondelectrode mount 30, respectively. Additionally, the deposition chamberframe 40 may include guide holes 44. Through the listed guide holes(i.e., guide holes 24, 26, 31, 36, and 44) may be placed guide pins 80.As shown in FIG. 2, the apparatus 1 may include four guide pins 80 thatmay be provided through guide holes 24, 26, 31, 36, and 44 in order toalign the various components of the apparatus 1.

The deposition chamber frame 40 is shown in FIGS. 1, 2, 6 and 7. Thedeposition chamber frame 40 may be disposed proximate to the firstelectrode mount 20 and the second electrode mount 30. More particularly,the deposition chamber frame 40 may be placed between the firstelectrode mount 20 and the second electrode mount 40, such that when theapparatus 1 is in its closed configuration, the first electrode mount20, the second electrode mount 30, and the deposition chamber frame 40may form a deposition chamber or vessel. For example, deposition chamberframe 40 may have a hollow interior as shown in FIG. 7 as cavity 401.The volume of cavity 401 may be filled with a deposition solution whenthe apparatus 1 is in the closed configuration.

The deposition chamber frame 40 may have a first aperture portion 41 anda second aperture portion 45.

First aperture portion 41 may be the portion of the deposition chamberframe 40 that may face the first electrode mount 20 and/or the firstelectrode 25. When the apparatus 1 is in its closed configuration, thefirst aperture portion 41 may abut the first electrode mount 20 or thefirst electrode 25 when the first electrode 25 is mounted at the firstelectrode mount 20. The first aperture portion 41 may include a firstaperture 411 and a conductive perimeter element 90. The conductiveperimeter element 90 may contact, and electrically communicate with, aportion of the first electrode 25. The conductive perimeter element 90may include at least one conductor or electrode contact that mayelectrically communicate with a portion of the first electrode 25. Forexample, the conductive perimeter element 90 may be a continuousconductor or electrode contact that may have a rectangular shape, asquare shape, a circular shape, an oval shape, or a combination thereof.Moreover, the conductive perimeter element 90 may be a continuousconductor or electrode contact that may have a shape configured to matcha lens (e.g., an electrochromic lens) or a shape suited to match theapplication for which the coated or plated substrate is to be used.

In another embodiment, the conductive perimeter element 90 may encompassa plurality of conductor or electrode contacts that may be arranged toprovide a rectangular shape, a square shape, a circular shape, an ovalshape, or a combination thereof. Moreover, the conductive perimeterelement 90 may be a plurality of conductor or electrode contacts thatmay be arranged to provide a shape configured to match a lens (e.g., anelectrochromic lens) or a shape suited to match the application forwhich the coated or plated substrate is to be used. In a preferredembodiment of the invention, the conductive perimeter element 90 may bea plurality of conductor or electrode contacts as set forth in FIGS. 2and 6.

As shown in FIGS. 2 and 6, the conductive perimeter element 90 may beset into the first aperture portion 41 of the deposition chamber frame40. The conductive perimeter element 90 may include a plurality ofelectrode contacts 91. Electrode contacts 91 may be deformable or biasedconducting pins. For example, electrode contacts 91 may be spring loadedconducting pins (e.g., POGO pins).

The conductive perimeter element 90 may also include a conductive base93 upon which the plurality of electrode contacts 91 may be connected.The conductive base 93 may be set into a base channel 94 on the firstaperture portion 41 of the deposition chamber frame 40. The conductivebase 93 may be connected to the deposition chamber frame 40 with one ormore fasteners. As shown in FIGS. 2 and 7, the conductive base 93 may befastened to the deposition chamber frame 40 in the base channel 94 withone or more screws, such as screws 92.

As shown in FIGS. 2 and 7, the deposition chamber frame 40 includes anelectrical connection tunnel 49 (see, e.g., inset 491 of FIG. 7). Theelectrical connection tunnel 49 communicates with a conductor 941 thatelectrically communicates with the conductive base 93. Accordingly, awire that may be connected to a power source or controller, as describedherein, may be passed through the electrical connection tunnel 49 tocontact the conductor 941 and allow a power source and/or a controllerto electrically communicate with the conductive base 93. Alternatively,element 941 may be an aperture through which a wire may be passed tocontact the conductive base 93.

The first aperture portion 41 may also include a gasket 42 that may beset into a gasket channel 43. The gasket 42 may be composed of aflexible, chemically inert material such as EPDM, silicone rubber, or acombination thereof. The gasket 42 may be provided to maintain a sealthat prevents leakage of deposition solution when the apparatus 1 is inits closed configuration (e.g., when the first electrode 25 is biasedagainst the first aperture portion 41 of deposition chamber frame 40).Moreover, the gasket 42 prevents contact between the conductiveperimeter element 90 and the deposition solution when the apparatus 1 isin its closed configuration. Accordingly, the perimeter of theconductive perimeter element 90 is preferably greater than the perimeterof the gasket 42.

In certain embodiments of the invention, the design of the the firstaperture 411 and the gasket 42 may be modified to act as a mask on thefirst electrode 25 to control the manner in which a coating or platingmaterial is deposited at the first electrode 25. For example, the firstaperture 411 and the gasket 42 may be sized to provide a rectangularshape, a square shape, a circular shape, an oval shape, or a combinationthereof. Moreover, the first aperture 411 and the gasket 42 may be sizedto provide a shape configured to match a lens (e.g., an electrochromiclens) or a shape suited to match the application for which the coated orplated material is to be used. For example, the first aperture 411 andthe gasket 42 may be sized to provide the shape of a motorcycle helmetvisor or spectacle lens. Indeed, the first electrode contact 25 may beused as a film or layer in an electrochromic device that may be appliedto a motorcycle helmet visor. Accordingly, the first aperture 411 andthe gasket 42 may be sized to match the shape of the visor to simplifyproduction where the first electrode is also sized to match theapplication for which the coated or plated substrate is to be used.

Second aperture portion 45 may be the portion of the deposition chamberframe 40 that may face the second electrode mount 30 and/or the secondelectrode 35. When the apparatus 1 is in its closed configuration, thesecond aperture portion 45 may abut the second electrode mount 30 or thesecond electrode 35 when the second electrode 35 is mounted at thesecond electrode mount 30. As shown in FIG. 7, the second apertureportion 45 may include a second aperture 451. The second aperture 451may be larger than the first aperture 411. For example, the secondaperture 451 may be at least about two times larger than the firstaperture 411. In addition, the second aperture 451 may be about threetimes larger than the first aperture 411.

Furthermore, the first aperture 411 and the second aperture 451 maydefine the front and back, respectively, of the cavity 401. The cavity401, between the first aperture 411 and the second aperture 451, may betelescoped, tapered, or a combination thereof. In certain specificembodiments, the cavity 401 tapers from the second aperture 451 to thefirst aperture 411 as shown, at least, in FIG. 7. More broadly, thedeposition chamber frame 40 may have a tapered or telescoped cavity 401,such that the counter electrode area is larger and/or significantlylarger (e.g., at least twice as large) than the working electrode area,so that limiting electrode processes do not occur at the counterelectrode.

The second aperture portion 45 may include a gasket 46 that may be setinto a gasket channel 47. The gasket 46 may be composed of a flexible,chemically inert material such as EPDM, silicone rubber, or acombination thereof. The gasket 46 may be provided to maintain a sealthat prevents leakage of deposition solution when the apparatus 1 is inits closed configuration (e.g., when the second electrode 35 is biasedagainst the second aperture portion 45 of the deposition chamber frame40).

As shown in FIG. 7, the deposition chamber frame 40 may include a frameinlet/outlet 48. The frame inlet/outlet 48 may be in fluid communicationwith a container 50. Specifically, the apparatus 1 may include a tube 51that connects the container 50 to the frame inlet/outlet 48. The frameinlet/outlet 48 allows the deposition chamber frame 40 to receive adeposition solution during a deposition process when the apparatus 1 isin its closed configuration. Moreover, the frame inlet/outlet 48 allowsthe deposition chamber frame 40 to empty of the deposition solutionafter a deposition process and before the apparatus 1 is reset to itsopen configuration.

The deposition chamber frame 40 may also include one or more ventapertures 61. The vent apertures 61 may communicate with the cavity 401of the deposition chamber frame 40. Moreover, the present invention mayinclude one or more stoppers 60 that may be placed into the ventapertures 61. The stoppers 60 may be composed of a flexible, chemicallyinert material such as EPDM, silicone rubber, or a combination thereof.

The present invention may also include a reference electrode 62 that maybe placed within the cavity 401 of the deposition chamber frame 40. Forexample, as shown in FIG. 2, at least one of the stoppers 60 may includea hole through which the reference electrode 62 may be provided.Therefore, when passing through a stopper 60, the reference electrode 62may be placed within the cavity 401 while maintaining the integrity ofthe cavity 401 and the deposition chamber frame 40. The referenceelectrode 60 may be any type of electrochemical reference orquasi-reference electrode known to those persons having ordinary skillin the art. However, in preferred embodiments, the reference electrode60 is a Ag/AgCl reference electrode or a Pt or Au wire quasi-referenceelectrode. Moreover, in particular embodiments, the reference electrode60 is configured to be placed within the cavity 401 of the depositionchamber frame 40 such that it may be proximate to the first electrode 25and the second electrode 35 when the apparatus 1 is in its closedconfiguration. Preferably, the reference electrode 60 is configured tobe placed within the cavity 401 of the deposition chamber frame 40 suchthat it may be closer to the first electrode 25 as compared to thesecond electrode 35 when the apparatus 1 is in its closed configuration.Indeed, the reference electrode 60 may be preferably disposed at aposition that is closer to the working electrode (i.e., the firstelectrode 25), compared to the counter electrode (i.e., the secondelectrode 35), such that the applied potential at the working electrodeis more accurately regulated.

As described herein, the apparatus 1 may include a container 50 that maybe fluidly connected to the deposition chamber frame 40 through a tube51. Specifically, a bottom portion of the container 50 may be connectedthrough the tube 51 to the frame inlet/outlet 48, which is preferablyplaced at the bottom of the deposition chamber frame 40, as shown inFIG. 7. The present invention allows for gravity flowing a depositionsolution contained in the container 50 from the container 50 in order tothe fill the cavity of the deposition chamber frame 40 when theapparatus 1 is in its closed configuration. As used herein, the term“gravity flowing,” relates to a flow of fluid that is driven by gravityfrom a higher location to a lower location. For example, filling thedeposition chamber frame 40 requires raising the container 50 above adesired fluid level in the deposition chamber frame 40. In contrast,emptying the deposition chamber frame 40 requires lowering the container50 below a desired fluid level in the deposition chamber frame 40. Dueto this arrangement, no pumps are required to fill or empty the cavity401 of the deposition chamber frame 40 when the apparatus 1 is in itsclosed configuration.

The deposition solution used in the processes of the invention mayinclude a solvent and one or more coating materials that may bedeposited or electroplated onto a first electrode 25 (i.e., thesubstrate). In certain embodiments, the coating material may include aninorganic coating material (e.g., one or more metal salts) or an organiccoating material (e.g., one or more monomers). Where the coatingmaterial includes an organic coating material, such as a monomer,deposition at the first electrode 25 (i.e., the substrate) may includeelectropolymerization. In preferred embodiments, the deposition solutionmay include monomers of electrochromic conducting polymers, for example,as may be described in U.S. Pat. Nos. 5,995,273 and 6,033,592; and U.S.Patent Application Publication Nos. 2013/0120821 and 2014/0268283.

The solvent of the deposition solution may include a polar aproticsolvent, a non-polar solvent, a polar protic solvent, or a combinationthereof, that may be known to a person having ordinary skill in the artprovided that the coating material is substantially miscible with thesolvent. In certain embodiments, the solvent of the deposition solutionis selected from the group consisting of acetonitrile,N,N′-dimethylformamide, and a combination thereof.

The present invention may also include a controller 70 that may be inelectrical communication with or otherwise may be configured to beelectrically connected to one or more of the first electrode 25, thesecond electrode 35, and the reference electrode 62. In certainpreferred embodiments, the controller 70 is provided to be connected tothe first electrode 25 (i.e., the working electrode) through theconductive perimeter element 90, the second electrode 35 (i.e., thecounter electrode) through the contact site 37, and the referenceelectrode 62. The controller 70 may be a potentiostat, a galvanostat, aDC power supply, or a combination thereof.

Preferably, the controller 70 may be a potentiostat/galvanostat asdescribed in pending U.S. patent application Ser. No. 14/844,367, theentirety of which is incorporated herein by reference.

Indeed, the controller 70 may be an electrochemical instrument that maybe provided for conducting electrochemical analysis of materials. Theelectrochemical instrument may be in the form of apotentiostat/galvanostat for conducting electrochemical analysis ofmaterials positioned between a counter electrode and a working electrodeof the instrument. The electrochemical instrument may include amicrocontroller, for controlling operation of the circuitry of theinstrument. The microcontroller may function to operate pursuant to acomputer program as well as various inputs from a user to providevarious or selected parameters or modes of operation. Themicrocontroller may produce desired digital control signals. Adigital-to-analog converter (DAC) may be provided in electricalcommunication with the microcontroller for generating an analog outputsignal in response to digital control signals from the microcontroller.A high current driver may be provided in electrical communication withthe DAC to produce a high current range output in response to the analogoutput signal from the DAC. For example, the high current driver mayproduce a high current range output in the range of about a fraction ofmilliAmpere mA or a mA to about amperes As. As a specific optionalexample, the high current driver may produce current in the range ofabout 0.25 mA to about 2.5 A. A high current monitor may be provided inelectrical communication with the high current driver to monitor thehigh current range output from the high current driver. The high currentmonitor may produce a feedback signal for the high current driver inresponse to the current monitored by the high current monitor to controlthe current produced by the high current driver. The high currentmonitor may also supply an output dependent on the current supplied fromthe high current driver for monitoring by the microcontroller. The highcurrent monitor may also supply a working output signal at a workingoutput for performing analysis of a selected material. For this purpose,a counter electrode contact may be provided for electrical communicationwith the counter electrode (e.g., second electrode 35) and connectablein electrical communication with the working output of the high currentmonitor. A working electrode contact may be provided for electricalcommunication with a working electrode (e.g., first electrode 25) andmay be electrically connectable with a fixed stable voltage potential(for example, ground or virtual ground) for enabling electrochemicalanalysis of material at or between the counter electrode and the workingelectrode. For example, a selected working output signal from the highcurrent monitor may be applied from the counter electrode at or throughthe material being analysed or tested and then to the working electrode.

A low current driver may also be optionally provided in electricalcommunication with the DAC to produce a low current range output inresponse to the analog output signal from the DAC. For example, a lowcurrent range output may be in the range of about nanoAmperes nAs, andperhaps even as small as picoAmperes pAs, to about a mA or a fraction ofa mA. As a specific optional example, the low current driver may producecurrent in the range of about 2.5 nA to 0.25 mA. The low current drivermay be in electrical communication with the counter electrode contact sothat the low current range output may be supplied by the low currentdriver to the counter electrode. A low current monitor may beconnectable in electrical communication with the working electrodecontact for detecting current at the working electrode contact. In a lowcurrent mode of operation, the low current range output from the lowcurrent driver may be supplied to the counter electrode through or atthe material being analysed or tested and then to the working electrode.The low current monitor in electrical communication with the workingelectrode may supply an output dependent on the current detected at theworking electrode contact for monitoring by the microcontroller. The lowcurrent monitor may also provide a feedback signal for the low currentdriver in order to control the output of the low current driver tocontrol the current between the counter electrode contact and theworking electrode contact. The low current monitor may optionallyinclude a monitor amplifier having an amplifier input connectable inelectrical communication with the working electrode contact and havingan amplifier output. The low current monitor may also include an arrayof feedback resistors connected between the output of the monitoramplifier and the input of the monitor amplifier. The low currentmonitor may also include a monitor multiplexer, for example, an analogmultiplexer, in electrical communication with the microcontroller forselecting at least one of the feedback resistors in the array forelectrical communication between the output and input of the monitoramplifier to control the output of the monitor amplifier.

The high current monitor may optionally include a first high currentrange monitoring circuit for monitoring current in a first high currentrange and a second high current monitoring circuit for monitoringcurrent in a second high current range. As an optional example, thefirst high current monitoring circuit may operate in a range of aboutmAs to about an A whereas the second high current monitoring circuit mayoperate in a range of about a fraction of a mA to about mAs. As a morespecific optional example, the high current monitoring circuit mayoperate in a range of about 25 mA to 2.5 A and the second high currentmonitoring circuit may operate in a range of about 0.25 mA to 25 mA. Ofcourse, the two ranges need not precisely overlap at a common end pointand such common end point can be altered to a different magnitude.

The instrument may also include a reference electrode contact forelectrical communication with a reference electrode (e.g., referenceelectrode 62) for positioning relative to the working electrode andcounter electrode in communication with the material, and a buffer inelectrical communication with the reference electrode contact fordetecting voltage at the reference electrode contact. The buffer maysupply an output dependent on the voltage detected at the referenceelectrode contact that is buffered from the reference electrode contactfor monitoring by the microcontroller. The buffer may also selectivelyprovide a feedback signal for the high current driver to control theoutput produced by the high current driver when operating in voltagemode at a high current or high power mode of operation in order tocontrol the voltage at the reference electrode contact. The buffer mayalso supply the feedback signal from the buffer to the low currentdriver to control the output produced by the low current driver tocontrol the voltage at the reference electrode contact when operating involtage mode at a low current or low power mode of operation. In orderto accommodate such an optional arrangement having both a high currentdriver and a low current driver, the instrument may also include a highcurrent switch for switchably connecting the high current driver in andout of electrical communication with the counter electrode contact and alow current switch for switchably connecting the low current driver inand out of electrical communication with the counter electrode contact.The microcontroller may function to enable or disable output from eitheror both of the high current or low current drivers to respectivelyprovide a type of high current switch and a low current switch,respectively, to connect and disconnect from the counter electrodecontact. The microcontroller may operate to control the high currentswitch and the low current switch so that when the high current switchelectrically connects the high current driver into electricalcommunication with the counter electrode contact, the microcontrollercauses the low current switch to switch the lower current driver out ofelectrical communication with the counter electrode contact. Likewise,when the low current switch switches the low current driver intoelectrical communication with the counter electrode contact, the highcurrent switch electrically disconnects the high current driver fromelectrical communication with the counter electrode contact. For anoptional arrangement in which the high current monitor includes both afirst high current monitoring circuit and a second high currentmonitoring circuit, the high current switch may include a first highcurrent monitor switch for electrically connecting the first highcurrent range monitoring circuit in and out of electrical communicationwith the counter electrode contact and a second high current monitoringswitch for electrically connecting the second high current monitoringcircuit in and out of electrical communication with the counterelectrode contact. In operation, the microcontroller may be inelectrical communication with the first and second high currentmonitoring switches such that when one of the high current monitoringswitches is turned on the other high current monitoring switch is turnedoff and when at least one of the high current monitoring switches isturned on then the low current switch is turned off under the control ofthe microcontroller.

The instrument may also include a ground switch under the control of themicrocontroller for electrically connecting the working electrodecontact in and out of electrical communication with a fixed stablevoltage potential such as ground or virtual ground. When the highcurrent driver is switched by the high current switch to be inelectrical communication with the counter electrode contact, such aswhen operating in a high power or high current mode of operation, themicrocontroller may control the ground switch to connect the workingelectrode contact to ground.

The instrument may also include a low current monitor switch under thecontrol of the microcontroller for switchably connecting the workingelectrode contact in and out of electrical communication with the lowcurrent monitor. In a low power or low current mode of operation, thelow current monitor switch electrically connects the working electrodecontact into electrical communication with the low current monitor andthe low current switch operates to connect the low current driver inelectrical communication with the counter electrode contact. In a highcurrent or high power mode of operation, the low current monitor switchmay also function to disconnect the working electrode contact out ofelectrical communication with the low current monitor, and the lowcurrent switch may function to disconnect the low current driver out ofelectrical communication with the counter electrode contact.

Next, the instrument may also include a feedback multiplexer, forexample, an analog multiplexer, in electrical communication with themicrocontroller and in electrical communication with the high currentmonitor for receiving the feedback signal from the high current monitor,the buffer for receiving the feedback signal from the buffer, and thelow current monitor for receiving the feedback signal from the lowcurrent monitor, and for switchably selecting which of the feedbacksignals, or a signal dependent thereon, is output by the feedbackmultiplexer under the control of the microcontroller. In this regard,the microcontroller may operate to control the feedback multiplexer tosupply the feedback signal from the high current monitor for the highcurrent driver when operating in high current mode and to supply thefeedback signal from the low current monitor for the low current driverwhen operating in low current mode, and to supply the feedback signalfrom the buffer for at least one of the high current driver or lowcurrent driver when operating in voltage mode. For example, the feedbackmultiplexer may supply the feedback signal from the buffer for the highcurrent driver when operating in voltage mode at a high power mode ofoperation and for the low current driver when operating in voltage modeat a low power mode of operation. Optionally, the first high currentrange monitoring circuit may provide a first high current feedbacksignal for the feedback multiplexer and the second high currentmonitoring circuit may supply a second high current feedback signal forthe feedback multiplexer. When operating in the high current mode, themultiplexer under the control of the microcontroller may selectivelysupply the first high current feedback signal from the first highcurrent range monitoring circuit for the high current driver whenoperating in first high current range and selectively supply the secondhigh current feedback signal from the second high current rangemonitoring circuit for the high current driver when operating in thesecond high current range. The first high current range monitoringcircuit may include a first sense resistor connected in series betweenthe high current driver and the counter electrode contact and a firstdifferential amplifier, such as an instrumentation amplifier, connectedacross the first sense resistor to detect the voltage produced by thecurrent flow through the first sense resistor to provide the first highcurrent feedback signal. Likewise, the second high current rangemonitoring circuit may include a second sense resistor connected inseries between the high current driver and the counter electrode and asecond differential amplifier, such as an instrumentation amplifier,connected across the second sense resistor to detect the voltageproduced by current flow through the second sense resistor to providethe second high current feedback signal. Preferably, the first andsecond sense resistors are connected in parallel circuits and havedifferent magnitudes of resistance, optionally such as a 10² magnitudedifference such as 0.1 and 10 ohms for example.

The instrument may also include an analog-to-digital converter (DAC) inelectrical communication with the outputs of the low current monitor,the buffer and the high current monitor to convert the output signals ofthe low current monitor, the buffer and the high current monitor todigital signals for the microcontroller.

In an optional arrangement, the buffer may also be in electricalcommunication with the counter electrode contact for detecting a voltageat the counter electrode contact and for supplying a buffered outputindicating the voltage at the counter electrode contact for electricalcommunication with the microcontroller.

The controller 70 may include an electrochemical instrument forconducting an electrochemical analysis of selected materials that may beconfigured, adjusted or set to operate in a high power or high currentmode of operation and as such may be in the configuration ofpotentiostat and/or galvanostat for providing selected electricalsignals to a counter electrode (e.g., second electrode 35) and a workingelectrode (e.g., first electrode 25). As configured for a high power orhigh current mode of operation, the electrochemical instrument mayinclude a microcontroller for providing digital control signals and adigital-to-analog converter (DAC) in electrical communication with themicrocontroller for generating an analog output signal in response todigital control signals from the microcontroller. A high current drivermay be in electrical communication with the DAC to produce a highcurrent range output in response to the analog output signal from theDAC. For example, the high current range output may be in the rangespreviously indicated. A high current monitor may be used in electricalcommunication with the high current driver to monitor the current outputby the high current driver. The high current monitor may produce acurrent feedback signal for the high current driver in response to thecurrent monitored by the high current monitor to control the currentproduced by the high current driver. The high current monitor may alsosupply an output dependent on the current produced by the high currentdriver for monitoring by the microcontroller. The high current monitormay also supply a working output signal at a work output for applicationto a material, such as a material under test or analysis. For thispurpose, a counter electrode contact for electrical communication with acounter electrode is connectable in electrical communication with thework output of the high current monitor. A working electrode contact forelectrical communication with a working electrode may be connected inelectrical communication with a fixed stable voltage potential, such asground or virtual ground, for enabling electrochemical analysis ofmaterial at or between the counter electrode and the working electrode.The high current monitor may optionally include a first high currentrange monitoring circuit for monitoring current in a first high currentrange and a second high current monitoring circuit for monitoringcurrent in a second high current range. For example, the first andsecond high current ranges may be in the ranges previously indicated.The high current monitor may also include a first high current monitorswitch for electrically connecting the first high current rangemonitoring circuit in and out of electrical communication with thecounter electrode and a second high current monitoring switch forelectrically connecting the second high current monitoring circuit inand out of electrical communication with the counter electrode contact,optionally under the control of the microcontroller which may be inelectrical communication with the first and second high currentmonitoring switches.

The instrument may also include a reference electrode contact forelectrical communication with a reference electrode (e.g., referenceelectrode 62) for positioning relative to the working electrode and thecounter electrode in communication with the material. A buffer may beprovided for electrical communication with the reference electrodecontact for detecting voltage at the reference electrode contact and forsupplying an output dependent on the voltage at the reference electrodecontact that is buffered from the reference electrode contact formonitoring by the microcontroller. The buffer may also provide afeedback signal for the high current driver to control the outputproduced by the high current driver to control the voltage at thereference electrode contact.

The instrument may also include a feedback multiplexer, optionally inthe form of an analog multiplexer, in electrical communication with themicrocontroller, and both in electrical communication with the highcurrent monitor for receiving the feedback signal from the high currentmonitor and in electrical communication with the buffer for receivingthe feedback signal from the buffer for switchably selecting under thecontrol of the microcontroller which of the feedback signals, or asignal dependent thereon, is output by the feedback multiplexer for thehigh current driver. In current mode, the microcontroller will switchthe feedback multiplexer to output the feedback signal from the highcurrent monitor for feedback for the high current driver. In voltagemode, the microcontroller will switch the feedback multiplexer to outputthe feedback signal from the buffer for feedback for the high currentdriver. Optionally, the first high current range monitoring circuit mayprovide a first high current feedback signal for the feedbackmultiplexer and the second high current range monitoring circuit mayprovide a second high current feedback signal for the feedbackmultiplexer. The feedback multiplexer may operate under the control ofthe microcontroller to selectively supply the first high currentfeedback signal, or a signal dependent thereon, from the first highcurrent range monitoring circuit for the high current driver whenoperating in the first high current range and to selectively supply thesecond high current feedback signal, or a signal dependent thereon, fromthe second high current range monitoring circuit for the high currentdriver when operating in the second high current range.

Optionally, the first high current range monitoring circuit may includea first sense resistor connected in series between the high currentdriver and the counter electrode contact, and a first differentialamplifier, such as an instrumentation amplifier, connected across thefirst sense resistor to detect the voltage generated by current flowthrough the first sense resistor to produce the first high currentfeedback signals and an output for monitoring by the microcontroller.Likewise, the second high current range monitoring circuit mayoptionally include a second sense resistor connected in series betweenthe high current driver and the counter electrode contact, and a seconddifferential amplifier, such as an instrumentation amplifier, connectedacross the second sense resistor to detect the voltage generated by thecurrent flow through the second sense resistor to produce the secondhigh current feedback signal and an output for monitoring by themicrocontroller. Preferably, the first and second sense resistors areconnected in parallel circuits and have different magnitudes ofresistance, optionally such as a 10² magnitude difference such as 0.1and 10 ohms for example.

The instrument may also include an analog-to-digital converter (ADC) inelectrical communication with the microcontroller and in electricalcommunication with the outputs of the buffer and the high currentmonitor to convert the output signals of the buffer and the high currentmonitor to a digital signal for the microcontroller.

Optionally, the buffer may also be connectable in electricalcommunication with the counter electrode contact for detecting a voltageat the counter electrode contact for supplying a buffered outputrepresenting the voltage at the counter electrode contact for electricalcommunication with the microcontroller.

The controller 70 may include an electromechanical instrument that maybe configured, adjusted, or set to operate, for example, as apotentiostat or a galvanostat in a low current or low power mode ofoperation. When so configured, the instrument includes a microcontrollerfor providing digital control signals, and a digital-to-analog converter(DAC) in electrical communication with the microcontroller forgenerating an analog output signal in response to digital controlsignals from the microcontroller. A low current driver may be positionedin electrical communication with the DAC to produce a low current rangeoutput in response to the analog output signal from the DAC. Forexample, a low current range may be in the range previously indicated. Acounter electrode contact may be provided for electrical communicationwith a counter electrode (e.g., second electrode 35) and for electricalcommunication with the output of the low current driver. A workingelectrode contact may also be provided in electrical communication witha working electrode (e.g., first electrode 25) for enablingelectrochemical analysis of material between the counter electrode andthe working electrode. In operation, current from the low current drivermay be supplied to the counter electrode for application at or throughthe material to be analyzed or tested and then to the working electrode.

The instrument may also include a low current monitor connectable inelectrical communication with the working electrode contact fordetecting current at the working electrode contact and for supplying anoutput dependent on the current detected at the working electrodecontact for monitoring by the microcontroller. The low current monitormay also provide a feedback signal for the low current driver in orderto control the output of the low current driver to control the currentbetween the counter electrode contact and the working electrode contact.The low current monitor may optionally include a monitor amplifier, suchas a current feedback amplifier or transimpedance amplifier, having aninput connectable in electrical communication with the working electrodecontact and providing an output. The low current monitor may alsoinclude an array of feedback resistors connected between the output ofthe monitor amplifier and the input of the monitor amplifier to providea feedback loop between the output and the input of the monitoramplifier. The low current monitor may also include a monitormultiplexer, for example, an analog multiplexer, in electricalcommunication with the microcontroller for selecting at least one of thefeedback resistors in the array for electrical connection between theoutput and the input of the monitor amplifier to control the output ofthe monitor amplifier.

The instrument may optionally include a reference electrode contact forelectrical communication with a reference electrode (e.g., referenceelectrode 62) for positioning relative to the working electrode and thecounter electrode in communication with the material. The instrument mayalso include a buffer for electrical communication with the referenceelectrode contact for detecting voltage at the reference electrodecontact. The buffer may function to supply an output dependent on thevoltage at the reference electrode contact that is buffered from thereference electrode contact for monitoring by the microcontroller. Thebuffer may also provide a feedback signal for the low current driver tocontrol the output produced by the low current driver to control thevoltage at the reference electrode contact. In a voltage mode ofoperation, the voltage at the reference electrode contact may bemonitored relative to voltage at the working electrode contact, whichmay, for example, be a virtual ground.

The instrument may also include a feedback multiplexer, for example, ananalog multiplexer, in electrical communication with themicrocontroller. The feedback multiplexer may also be in electricalcommunication with the buffer for receiving the feedback signal from thebuffer and in electrical communication with the low current monitor forreceiving the feedback signal from the low current monitor forswitchably selecting which of the feedback signals input to the feedbackmultiplexer, or a signal dependent thereon, will be output for the lowcurrent driver under the control on the microcontroller. In this regard,the microcontroller may function to control the feedback multiplexer tosupply the feedback signal from the low current monitor for the lowcurrent driver when operating in low current mode and to selectivelysupply the feedback signal from the buffer for the low current driverwhen operating in voltage mode.

The instrument may also include an analog-to-digital converter (ADC) inelectrical communication with the microcontroller and in electricalcommunication with the outputs of the low current monitor and the bufferto convert the output of the low current monitor and the buffer to adigital signal for supply to the microcontroller for monitoring by themicrocontroller.

Optionally, the buffer may also be connectable in electricalcommunication with the counter electrode contact for detecting a voltageat the counter electrode contact and for supplying a buffered outputrepresenting the voltage at the counter electrode contact for electricalcommunication with the microcontroller.

The controller 70 may include or be connected to a power source 75. Thepower source 75 may include any source of direct current (DC) to thecontroller 70. In certain embodiments, the power source 75 could includea source of alternating current (AC) that is converted to DC, as isknown in the art. The power source 75 may include a battery. As usedherein, the term “battery” refers to an electro-chemical devicecomprising one or more electro-chemical cells and/or fuel cells, and soa battery may include a single cell or plural cells, whether asindividual units or as a packaged unit.

The present invention also includes method 1000, shown in FIG. 8, ofusing the apparatus 1 to produce a working electrode (e.g., firstelectrode 25) having a coating material deposited or otherwiseelectroplated thereon.

The apparatus 1 may be provided in the open configuration (step 1010) sothat a first electrode 25 (i.e., the working electrode) may be mountedon the first electrode mount 20 (step 1020) and a second electrode 35(i.e., the counter electrode) may be mounted on the second electrodemount 30 (step 1030).

Prior to providing the deposition solution, a deposition chamber may beprepared by activating the biasing members 16 to bias (1) the workingelectrode against the first aperture portion 41 of the depositionchamber frame 40; and (2) the counter electrode against second apertureportion 45 of the deposition chamber frame 40, and thereby hermeticallysealing the deposition chamber (step 1040). As noted above, the counterand working electrodes (i.e., first and second electrodes 25 and 35,respectively) then form the two walls of the deposition chamber. Incertain embodiments, the deposition chamber may be prepared andhermetically sealed by with pneumatic actuators 16, which may applyabout 75 psi of pressure on the back of the working electrode. Step 1040may further include providing a reference electrode 62 (e.g., a Ag/AgClreference electrode or Pt or Au wire quasi reference electrode) to thedeposition chamber at the deposition chamber frame 40.

A deposition solution may then be provided to the deposition chamber bygravity flowing the deposition solution into the deposition chamber(step 1050). Gravity flowing the deposition solution eliminates pumpsand extensive circulation tubing that may ordinarily be required. Acontainer 50 that holds the deposition solution is connected to thedeposition chamber frame 40, which forms a portion of the depositionchamber, and is raised above the level of the deposition chamber togravity flow the deposition solution into the deposition chamber.

A controller 70, which may be a potentiostat, galvanostat, orcombination thereof, may then be connected to the working electrode,counter electrode, and reference electrode and a potential may beapplied across the working electrode and the counter electrode (step1060). Through the application of a potential across the working andcounter electrodes in a galvanostatic or potentiostatic mode,electrochemical deposition may occur at the working electrode whereinthe coating material in the deposition solution may be deposited at theworking electrode. Electrochemical deposition may be carried outpreferably in a potentiostatic (i.e., with controlled voltage) ratherthan a galvanostatic (i.e., controlled current) mode for electrochromicCPs of the invention as described, for example, in U.S. PatentApplication Publication No. 2013/0120821, the entirety of which isincorporated herein by reference.

In certain embodiments of the invention, the manner in which thepotential may be applied may be dependent upon the specificelectrochromic CP being deposited and may be tailored thereto. Forexample, in the case of poly (aromatic amine) CPs, generally, apotentiostatic method with coulometric monitoring of the total chargedeposited (i.e., step 1070), may be preferred. In this manner, thecharge deposited per unit area may be used to control the thickness,morphology, and other parameters of the film of electrochromic CPdeposited. In the case of thiophene-based CPs, generally, arepeated-potential-sweep method, starting and stopping at preferred,predetermined voltages, is preferred.

Therefore, step 1060 may include applying a linear scan appliedpotential, which may include scanning the applied potential from apre-determined initial potential to a pre-determined final potential ata pre-determined scan rate. Step 1060 may, alternatively, includeapplying a fixed applied potential or several fixed applied potentialsacross the working electrode and the counter electrode. The fixedapplied potential(s) may be applied until (1) a pre-determined totalcharge is achieved, or (2) a pre-determined total deposition time haselapsed.

Accordingly, the controller 70 may be provided to control theapplication of potential across the working and counter electrodes. Thecontroller 70 may terminate or halt the electrochemical depositionprocess when the desired voltage, number of linear potential sweeps,total charge, or a combination of selected parameters, is achieved (step1080).

After halting the application of potential across the working electrodeand counter electrode (step 1080), the deposition solution may beremoved from the deposition chamber (step 1090). To remove thedeposition solution from the deposition chamber, the container 50 islowered below the level of the deposition chamber. The fill/emptyprocess may be automated using an actuator that may be provided toautomatically raise the container or lower the container when actuatedto fill or empty the vessel, respectively.

After the deposition solution is removed from the deposition chamber(step 1090), the biasing members 16 may be deactivated (e.g., releasingthe pneumatic pressure at pneumatic actuators 16) and the firstelectrode mount 20, second electrode mount 30, and deposition chamberframe 40 may be separated to open the deposition chamber (step 1100).When the apparatus 1 is in its open configuration, the working electrodewith coating material deposited thereon may be removed for furtherprocessing (step 1110).

Upon removing the working electrode with the coating material depositedthereon, the apparatus 1 may be recycled and returned to step 1020 torepeat the process in order to produce another coated or electroplatedsubstrate. Moreover, when repeating the method 1000, the counterelectrode may be cleaned before remounting the counter electrode at thesecond electrode mount 30 in step 1030. Alternatively, when repeatingthe method 1000, step 1030 may be omitted and the counter electrode neednot be removed between cycles of the method.

The entire deposition process, including, for example, the steps such asloading of the substrate (i.e., working electrode), charging of thedeposition solution, deposition via an applied-potential, draining ofthe deposition solution, and removal of the deposited substrate, isamenable to and is easily automated or semi-automated.

A number of patent and non-patent publications are cited herein in orderto describe the state of the art to which this invention pertains. Theentire disclosure of each of these publications is incorporated byreference herein.

While certain embodiments of the present invention have been describedand/or exemplified above, various other embodiments will be apparent tothose skilled in the art from the foregoing disclosure. The presentinvention is, therefore, not limited to the particular embodimentsdescribed and/or exemplified, but is capable of considerable variationand modification without departure from the scope and spirit of theappended claims.

Moreover, as used herein, the term “about” means that dimensions, sizes,formulations, parameters, shapes and other quantities andcharacteristics are not and need not be exact, but may be approximateand/or larger or smaller, as desired, reflecting tolerances, conversionfactors, rounding off, measurement error and the like, and other factorsknown to those of skill in the art. In general, a dimension, size,formulation, parameter, shape or other quantity or characteristic is“about” or “approximate” whether or not expressly stated to be such. Itis noted that embodiments of very different sizes, shapes and dimensionsmay employ the described arrangements.

Furthermore, the transitional terms “comprising”, “consistingessentially of” and “consisting of”, when used in the appended claims,in original and amended form, define the claim scope with respect towhat unrecited additional claim elements or steps, if any, are excludedfrom the scope of the claim(s). The term “comprising” is intended to beinclusive or open-ended and does not exclude any additional, unrecitedelement, method, step or material. The term “consisting of” excludes anyelement, step or material other than those specified in the claim and,in the latter instance, impurities ordinary associated with thespecified material(s). The term “consisting essentially of” limits thescope of a claim to the specified elements, steps or material(s) andthose that do not materially affect the basic and novelcharacteristic(s) of the claimed invention. All devices, apparatuses,and methods described herein that embody the present invention can, inalternate embodiments, be more specifically defined by any of thetransitional terms “comprising,” “consisting essentially of,” and“consisting of.”

What is claimed is:
 1. An electrochemical deposition apparatus,comprising: a. a support structure; b. a first electrode mount connectedto the support structure; c. a second electrode mount connected to thesupport structure; and d. a deposition chamber frame configured toreceive a deposition solution and disposed proximate to the first andsecond electrode mounts, the deposition chamber frame comprising: i. afirst aperture portion configured to face the first electrode mount, thefirst aperture portion comprising a first aperture and a conductiveperimeter element; and ii. a second aperture portion configured to facethe second electrode mount, the second aperture portion comprising asecond aperture.
 2. The apparatus of claim 1, comprising at least onebiasing member that connects the support structure to at least one ofthe first electrode mount and the second electrode mount.
 3. Theapparatus of claim 2, wherein the at least one biasing member comprisesa spring, a clamp, an actuator, or a combination thereof.
 4. Theapparatus of claim 2, wherein the at least one biasing member connectsthe support structure to the first electrode mount and comprises apneumatic actuator.
 5. The apparatus of claim 1, wherein the secondaperture is larger than the first aperture.
 6. The apparatus of claim 1,comprising a first electrode connected to the first electrode mount andconfigured to be disposed in electrical communication with theconductive perimeter element.
 7. The apparatus of claim 6, wherein thefirst electrode comprises a material selected from the group consistingof indium-tin-oxide (ITO), poly (ethylene terephthalate) (PET), glass,and a combination thereof.
 8. The apparatus of claim 6, wherein thefirst electrode comprises a conductive sheet.
 9. The apparatus of claim1, wherein the conductive perimeter element comprises at least oneelectrode contact.
 10. The apparatus of claim 9, wherein the at leastone electrode contact comprises a plurality of electrode contacts. 11.The apparatus of claim 10, wherein the plurality of electrode contactscomprises a plurality of spring-loaded contact pins.
 12. The apparatusof claim 1, comprising a second electrode connected to the secondelectrode mount.
 13. The apparatus of claim 12, wherein the secondelectrode comprises one or more of graphite, gold, and platinum.
 14. Theapparatus of claim 12, wherein the second electrode comprises aconductive sheet.
 15. The apparatus of claim 1, comprising a controllerin electrical communication with the conductive perimeter element. 16.The apparatus of claim 1, comprising first and second electrodesconnected to the first and second electrode mounts, respectively,wherein the first electrode comprises a working electrode and the secondelectrode comprises a counter electrode.
 17. The apparatus of claim 16,comprising a controller in electrical communication with the conductiveperimeter element and the counter electrode.
 18. The apparatus of claim1, comprising a reference electrode configured to be disposed within thedeposition chamber frame.
 19. The apparatus of claim 18, wherein thereference electrode comprises one or more of an Ag/AgCl referenceelectrode, a Pt wire quasi-reference electrode, and an Au wirequasi-reference electrode.
 20. The apparatus of claim 1, comprising acontainer in fluid communication with the deposition chamber frame;wherein the container is configured to contain a deposition solutionthat comprises a coating material.
 21. An electrochemical depositionapparatus comprising an electroplating vessel, the apparatus comprising:a. a support structure; b. a frame disposed within the support structureand comprising a cavity configured to receive a deposition solution, thecavity comprising: i. a first aperture portion comprising a firstaperture; and ii. a second aperture portion comprising a secondaperture, wherein the second aperture is larger than the first aperture;c. a working electrode disposed proximate to the first aperture; and d.a counter electrode disposed proximate to the second aperture; whereinthe frame, the working electrode, and the counter electrode combine toform the electroplating vessel.
 22. The apparatus of claim 21, whereinthe cavity comprises a telescoped cavity, a tapered cavity, or acombination thereof.
 23. The apparatus of claim 21, wherein the secondaperture is at least twice as large as the first aperture.
 24. Theapparatus of claim 21, comprising a plurality of guides that areconfigured to align the frame, the working electrode, and the counterelectrode.
 25. A method for electrochemically depositing a coatingmaterial on a working electrode with the electrochemical depositionapparatus of claim 1, the method comprising the steps of: a. mounting aworking electrode at the first electrode mount; b. mounting a counterelectrode at the second electrode mount; c. preparing a depositionchamber by: i. biasing the working electrode against the first apertureportion of the deposition chamber frame; and ii. biasing the counterelectrode against the second aperture portion of the deposition chamberframe; e. providing a deposition solution to the deposition chamber,wherein the deposition solution comprises a coating material; f applyinga potential across the working electrode and the counter electrode toelectrochemically deposit the coating material at the working electrode;and g. removing the working electrode, having the coating materialdeposited thereon, from the first electrode mount.
 26. The method ofclaim 25, wherein the step of providing the deposition solution to thedeposition chamber comprises gravity flowing the deposition solution tothe deposition chamber from a container that is in fluid communicationwith the deposition chamber by raising the container above thedeposition chamber.
 27. The method of claim 25, wherein the step ofremoving the working electrode comprises removing the depositionsolution from the deposition chamber by gravity flowing the depositionsolution to the container from the deposition chamber by lowering thecontainer below the deposition chamber.
 28. The method of claim 25,wherein the step of applying a potential across the working electrodeand counter electrode comprises applying a linear scan appliedpotential, which comprises scanning the applied potential from apre-determined initial potential to a pre-determined final potential ata pre-determined scan rate.
 29. The method of claim 25, wherein the stepof applying a potential across the working electrode and counterelectrode comprises applying a fixed applied potential, which comprisesapplying a pre-determined fixed potential until: i. a pre-determinedtotal charge is achieved; or ii. a pre-determined total deposition timehas elapsed.
 30. The method of claim 25, wherein the step of preparingthe deposition chamber comprises at least one of: i. pneumaticallybiasing the working electrode against the first aperture portion of thedeposition chamber frame; and ii. pneumatically biasing the counterelectrode against the second aperture portion of the deposition chamberframe.